TW201341334A - Low CTE, ion-exchangeable glass compositions and glass articles comprising the same - Google Patents

Abstract

Glass compositions and glass articles comprising the glass compositions are disclosed. In one embodiment, a glass composition includes from about 65 mol.% to about 70 mol.% SiO2; from about 9 mol.% to about 14 mol.% Al2O3; and from about 0 mol.% to about 11 mol.% B2O3 as glass network formers. The glass composition also includes from about 5 mol.% to less than 10 mol.% alkali oxide R2O, wherein R is at least one of Li, Na, and K. The glass composition also includes from about 3 mol.% to about 11 mol.% of divalent oxide MO, wherein M is at least one of Mg, Ca, Ba, SrO and Zn. The glass composition has a coefficient of thermal expansion which is less than or equal to 55*10<SP>-7</SP>/ DEG C and is amenable to strengthening by ion-exchange. The glass composition is well suited for use as the glass cladding layers of a laminated glass article.

Description

Low CTE ion exchangeable glass composition and glass articles containing the same [Reciprocal Reference of Related Applications]

This application claims the benefit of priority to U.S. Provisional Application Serial No. 61/604,833, filed on Jan. 29, 2012. This application is based on the content of this application, the entire content of which is hereby incorporated by reference.

The present invention relates generally to glass compositions, and more particularly to glass compositions having relatively low average CTE and subjected to ion exchange strengthening and glass articles comprising such glass compositions.

Glass articles such as cover glass, glass backsheets, and the like are used in both consumer and commercial electronic devices such as LCD and LED displays, computer monitors, automated teller machines (ATMs), and the like. Some of these glass objects may include "touch" functionality that necessitates contact with glass objects by various objects, including the user's fingers and/or stylus devices, and as such In other words, the glass must be strong enough to withstand normal contact without damage. In addition, this Glass-like objects can also be incorporated into portable electronic devices such as mobile phones, personal media players, and tablets. Glass articles incorporated into such devices can be susceptible to damage during transport and/or use of associated devices. Therefore, glass articles used in electronic devices may require enhanced strength to be able to resist not only the "touch" contact from actual use, but also the accidental contact and impact that may occur when transporting the device.

Various processes can be used to strengthen glass objects, including chemical tempering, thermal tempering, and lamination. Chemical tempering generally involves exchanging smaller alkali ions (such as lithium ions and/or sodium ions) in a glass article into larger ones by immersing the glass article in a molten salt bath containing larger alkali ions. Alkali ion (such as potassium ion). Thus, to facilitate chemical tempering or ion exchange processes, the glass article generally comprises a relatively high concentration of alkali ions.

The presence of alkali ions in the glass article generally increases the average coefficient of thermal expansion of the glass article, and in this regard, the glass article may not be suitable for use in glass articles that require a relatively low average coefficient of thermal expansion (such as overlay-reinforced glass articles). In the application of glass).

Accordingly, there is a need for alternative glass compositions that have a relatively low average coefficient of thermal expansion and that are also enhanced by ion exchange and glass articles incorporating such glass compositions.

According to one embodiment, the glass composition comprises from about 65 mole % to about 70 mole % SiO ₂ as a glass network former, from about 9 mole % to about 14 mole % Al ₂ O ₃ and From about 0 mole % to about 11 mole % B ₂ O ₃ . The glass composition may also include from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K. The glass composition may also include from about 3 mole % to about 11 mole % of the divalent oxide MO, wherein M is at least one of Mg, Ca, Ba, and Zn. The glass composition generally has an average coefficient of thermal expansion of the glass formed from the glass composition, the average coefficient of thermal expansion being less than or equal to 55 x 10 ^-7 / ° C, and ion exchange in a 100% KNO ₃ salt bath at 410 ° C for 8 hours. The compressive stress in the subsequent glass composition is greater than or equal to 400 MPa, and the liquidus viscosity is greater than or equal to 35 kPoise. Due to the relatively low average coefficient of thermal expansion, the glass composition is particularly well suited for use as a glass cover for laminated glass articles such as laminated glass articles formed by a melt lamination process.

In one embodiment, the glass article includes a glass core layer disposed between the first glass cover layer and the second glass cover layer. In some such embodiments, the core glass can have a first surface and a second surface opposite the first surface, wherein the first glass cover layer can be fused to the first surface of the glass core layer and the second glass cover layer It can be fused to the second surface of the glass core layer. In other embodiments, a first diffusion glass layer may be disposed between the glass core layer and the first glass cover layer; in addition, a second diffusion glass layer may be disposed between the glass core layer and the second glass cover layer; These diffusion layers can be formed during the fusion formation process. Forming a first glass cover layer and a second glass cover layer from the glass composition, the glass composition may include from about 55 mole % to about 70 mole % SiO ₂ , from about 9 mole % to about 14 moles % Al ₂ O ₃ and from about 0 mole % to about 11 mole % B ₂ O ₃ . The glass composition may further comprise from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K. The glass cover layer may further comprise from about 3 mole % to about 11 mole % of the divalent oxide MO, wherein M is at least one of Mg, Ca, Ba, and Zn. The glass composition generally has an average coefficient of thermal expansion of less than or equal to 55 x 10 ^-7 / ° C and is subjected to ion exchange strengthening.

Additional features and advantages of the glass composition and the glass article comprising the glass composition will be set forth in the detailed description which follows, and those skilled in the <RTIgt; The embodiments, including the following detailed description, claims and drawings, identify additional features and advantages.

It is to be understood that the foregoing general description of the embodiments of the invention The figures are included to provide a further understanding of the various embodiments and are incorporated in and constitute a part of this specification. BRIEF DESCRIPTION OF THE DRAWINGS The various embodiments described herein are used in connection with the description and the

100‧‧‧ laminated glass objects

102‧‧‧ glass core layer

104a‧‧‧glass cover

104b‧‧‧glass cover

200‧‧‧Laminated melt drawing equipment

202‧‧‧Insulation pipe

204‧‧‧Under heat pipe

206‧‧‧fused glass covering composition

208‧‧‧fused glass core composition

210‧‧‧ slots

212‧‧‧ slot

216‧‧‧External forming surface

218‧‧‧External forming surface

220‧‧‧ root

222‧‧‧ Externally formed surface

224‧‧‧External forming surface

Fig. 1 is a view schematically showing an average thermal expansion coefficient (y-axis) of a glass composition as a function of an alkali metal oxide concentration (x-axis) contained in a glass composition; The compressive stress (y-axis) of the composition as a function of the alkali metal oxide concentration (x-axis) contained in the glass composition after ion exchange for 8 hours in a KNO ₃ salt bath at 410 ° C; 3 graphically depicts the layer depth and the average coefficient of thermal expansion (y-axis) of the glass composition after ion exchange for 8 hours in a KNO ₃ salt bath at 410 ° C, the layer depth and the average coefficient of thermal expansion as a glass composition Substituting a function of ZnO (x-axis) of CaO; FIG. 4 schematically depicts a cross-section of a laminated glazing article according to one or more embodiments shown and described herein; and FIG. 5 is schematically depicted for A melt drawing process for producing the glass article of Fig. 4.

Reference will now be made in detail to embodiments of glass compositions having a low coefficient of thermal expansion and glass articles incorporating the glass compositions, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numerals will be used to refer to the The glass compositions described herein generally have a relatively low coefficient of thermal expansion, and in this regard, the glass compositions can be used in conjunction with the core glass composition to produce laminated glass articles having relatively high thermal expansion. The coefficients of the laminated glass articles are compressively stressed without ion exchange or thermal tempering. The glass compositions described herein are also subjected to further strengthening by ion exchange to increase surface compression in the glass. In one embodiment, the glass composition can comprise from about 65 mole % to about 70 mole % SiO ₂ as a glass network former, from about 9 mole % to about 14 mole % Al ₂ O ₃ and B ₂ O ₃ from about 0% by mole to about 11% by mole. The glass composition may also include from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K. The glass composition may also include from about 3 mole % to about 11 mole % of the divalent oxide MO, wherein M is at least one of Mg, Ca, Ba, and Zn. The glass composition generally has an average coefficient of thermal expansion of less than or equal to 55 x 10 ^-7 / ° C. The glass composition and the laminated glass article comprising the glass composition are further described herein with particular reference to the accompanying drawings.

The term "liquid viscosity" as used herein refers to the shear viscosity of a glass composition at the liquidus temperature of the glass composition; as used herein, the term "liquidus temperature" refers to the presence of a counter in the glass composition. The highest temperature for vitrification; as used herein, the term "CTE" refers to the coefficient of thermal expansion of a glass composition that is averaged over a temperature range of from about 20 °C to about 300 °C.

Unless otherwise indicated, in the examples of the glass compositions described herein, the concentrations of the constituent components (eg, SiO ₂ , Al ₂ O ₃ , B ₂ O _{3 ,} etc.) are designated as molybdenum based on the oxide. Percentage (% by mole).

As will be described in further detail herein, a reinforced laminated glazing article can be formed by melting a glass cover layer having a relatively low average coefficient of thermal expansion to a glass core layer having a relatively high average coefficient of thermal expansion. When the laminate structure is cooled, the difference in thermal expansion coefficient between the glass core layer and the glass cover layer produces a compressive stress in the glass cover layer. Although the compressive stress extends deeply into the cover glass layer of the laminated glass article, the compressive stress at the surface of the laminated glass article is generally low, requiring the laminated glass article to be ion exchange reinforced to achieve the desired Surface compression. However, since it is necessary to promote the ion exchange-enhanced alkali ion to substantially increase the average thermal expansion coefficient of the glass, it is difficult to manufacture a glass composition having a thermal expansion coefficient suitable for use as a glass cover layer and undergoing ion exchange strengthening, thereby making the glass unsuitable. As a glass cover layer in a laminated object. The glass compositions disclosed herein have a relatively low CTE and are also subjected to ion exchange strengthening, and as such, such glass compositions are suitable for use as a glass cover layer in laminated glass articles.

In the examples of the glass compositions described herein, SiO ₂ is the largest composition of the composition, and as such, SiO ₂ is the major component of the glass network. When the concentration of SiO _{2 in} the glass composition is low (i.e., less than about 55 mol%), the resulting glass has low chemical durability. In addition, the resulting glass may have a low liquid viscosity which renders the glass unsuitable for melt formation, such as using a melt down draw process and/or a melt layer press process. However, if the concentration of SiO _{2 in the} glass composition is too high (i.e., greater than about 70 mol%), the formability of the glass composition can be weakened because the higher SiO ₂ concentration increases the difficulty of melting the glass. Turning adversely affects the formability of the glass. The embodiments herein described embodiment, the glass composition is substantially a concentration of greater than or equal to about 55 mole% and less than or equal to about 70 mole% of SiO _2, in order to facilitate formation of the molten glass composition. In some embodiments, the SiO ₂ concentration in the glass composition is greater than or equal to about 65 mole percent and less than or equal to about 70 mole percent. In other embodiments, the amount of SiO ₂ in the glass composition is greater than or equal to about 65 mole percent and less than or equal to about 68 mole percent. In some other embodiments, the glass composition comprises a concentration of from about 63 mole% to about 66 mole% of SiO _2.

The glass compositions described herein also comprise Al ₂ O ₃ . Al ₂ O _{3 is} used as a glass network former, similar to SiO ₂ . Like SiO ₂ , Al ₂ O ₃ increases the viscosity of the glass composition due to the major tetrahedral coordination of Al ₂ O ₃ in the glass melt formed by the glass composition. Further, an increase in the Al ₂ O ₃ concentration of the glass composition relative to the alkali metal oxide or alkaline earth metal oxide substantially reduces the CTE of the glass composition and increases the durability of the glass composition. Al ₂ O ₃ also improves the ion exchange performance of the glass composition by increasing the strain point of the glass and increasing the diffusion of alkali ions in the glass network. Thus, the presence of Al ₂ O ₃ improves the kinetics of the ion exchange process and increases the maximum compressive stress that may be obtained. However, when the glass composition is the total concentration of alkali metal oxides is less than the concentration of Al ₂ O _3, Al ₂ O ₃ was added to reduce the fact that it can be reached via ion exchange of compressive stress and depth of layer.

In embodiments of the glass compositions described herein, the Al ₂ O ₃ concentration in the glass composition is substantially less than or equal to about 15 mole % to achieve a glass composition having the desired low CTE and ion exchange performance. . For example, in some embodiments, the Al ₂ O ₃ concentration in the glass composition is greater than or equal to about 9 mole % and less than or equal to about 14 mole %. In some embodiments, the Al ₂ O ₃ concentration in the glass composition can be greater than or equal to about 10 mole % and less than or equal to about 13 mole %. In some other embodiments, the Al ₂ O ₃ concentration can be greater than or equal to about 10 mole % and less than or equal to about 12 mole %.

The glass composition described herein also includes an alkali metal oxide R ₂ O wherein R is Li, Na, K or a combination of Li, Na, K. In the embodiments described herein, the alkali metal oxide lowers the melting temperature of the glass and the liquidus temperature, thereby improving the formability of the glass composition. However, the alkali metal oxide increases the CTE of the glass composition and simultaneously improves the ion exchange efficiency relative to other oxides included in the glass. For example, Figure 1 graphically depicts the CTE (y-axis) of a glass composition as a function of alkali metal oxide concentration (x-axis). As shown in Fig. 1, the CTE of the glass composition generally increases as the concentration of the alkali metal oxide increases. Typically, K ₂ O Na ₂ O generally increase substituted CTE glass, Li ₂ O and Na ₂ O substituent reduced CTE. Thus, the presence of smaller alkali ions in the glass results in a smaller increase in CTE.

Similarly, Figure 2 graphically depicts the compressive stress (y-axis) of the glass composition after ion exchange for 8 hours in a KNO ₃ salt bath at 410 ° C as the alkali metal oxide concentration (x-axis) ) function. As shown in Figure 2, the compressive stress that can be achieved via ion exchange generally increases with increasing alkali metal oxide concentration. In particular, ion exchange is substantially facilitated by exchanging smaller alkali ions (such as Li ⁺ or Na ⁺ ) in the glass with larger alkali ions (such as K ⁺ ) in the molten salt bath. Three types of ion exchange occurs generally: to exchange Na ⁺ Li ^+, the switch outputs a deep depth, but low compressive stress; to exchange K ⁺ Li ^+, the output of the switch a small depth, but a relatively large compression Stress; and exchange of Na ⁺ with K ⁺ , which produces a medium layer depth with moderate compressive stress. In embodiments where the glass composition is used as a glass cover layer in a laminated laminated glass article, the compressive stress has a primary interest because a high layer depth can be achieved in the glass cover layer via a lamination process. Therefore, the glass composition of composition as described herein in the alkali metal oxide will generally comprise greater than the concentration of K ₂ O and Li ₂ O ₂ O concentration Na, in order to facilitate exchange of Li ⁺ and K ⁺ / K ⁺ exchange or Na ⁺ to obtain maximum surface compression.

In the embodiments described herein, the total concentration of alkali metal oxide R ₂ O in the glass composition is substantially less than about 10 mole %. For example, in some embodiments, the glass compositions in an R ₂ O concentration is greater than or equal to about 5 mole% and less than or equal to about 10 mole%. In some other embodiments, R ₂ O concentration is greater than or equal to about 6 mole percent and less than or equal to about 9% mole.

In embodiments described herein, the alkali metal oxide R ₂ O can include at least one of Li ₂ O, Na ₂ O, and K ₂ O. Na ₂ O may be present in the glass composition at a concentration greater than or equal to about 0 mole % and less than or equal to about 10 mole % or even at a concentration greater than or equal to about 7 mole % and less than or equal to about 12 mole % in. Li ₂ O may be present in the glass composition at a concentration greater than or equal to about 0 mole % and less than or equal to about 7 mole % or even at a concentration greater than or equal to about 5 mole % and less than or equal to about 10 mole % in. K ₂ O may be present in the glass composition at a concentration greater than or equal to about 0 mole % and less than or equal to about 2 mole % or even at a concentration greater than or equal to about 1 mole % and less than or equal to about 3 mole % in.

If the glass compositions described herein are limited to SiO ₂ , Al ₂ O ₃ and the alkali metal oxides as described above, the viscosity of the composition will be too high to be suitable for melt formation. Accordingly, the glass compositions described herein include additional constituent components to ensure good melt quality and melt formability. The composition may include B ₂ O ₃ and a divalent cation oxide such as MgO, CaO, SrO, BaO, and ZnO, and the B ₂ O ₃ and the divalent cation oxide act as a flux to reduce the melting temperature of the glass composition.

The glass composition in the embodiments described herein may further comprise B ₂ O ₃ . Like SiO ₂ and Al ₂ O ₃ , B ₂ O ₃ contributes to the formation of a glass network. B ₂ O _{3 is} added to the glass composition to reduce the viscosity of the glass composition and the liquidus temperature. In particular, depending on the particular composition of the glass, an increase in B ₂ O ₃ concentration of 1 mol% reduces the temperature required to obtain an equivalent viscosity of 10 ° C to 14 ° C. However, B ₂ O ₃ can lower the liquidus temperature of the glass composition from 18 ° C to 22 ° C per mol % of B ₂ O ₃ . In this regard, B ₂ O ₃ reduces the liquidus temperature of the glass composition more rapidly than B ₂ O ₃ reduces the liquid viscosity of the glass composition, effectively increasing the liquid phase viscosity. B ₂ O ₃ can be added to the glass composition to soften the glass network with minimal impact on the CTE. Therefore, B ₂ O ₃ is useful for improving the melting efficiency without increasing CTE. The addition of B ₂ O ₃ to the glass composition also reduces the Young's modulus of the glass composition and improves the inherent damage resistance of the glass. However, the addition of B ₂ O ₃ reduces the diffusivity of ions in the glass network and thus negatively affects ion exchange performance and substantially reduces the amount of compressive stress that can be achieved.

In the embodiments described herein, B ₂ O _{3 is present} substantially in the glass composition in an amount less than or equal to about 10 mole % in order to promote good melting performance without significantly weakening the ion exchange efficiency of the glass. . For example, in some embodiments, B ₂ O ₃ is present in the glass composition at a concentration greater than or equal to about 0 mole percent and less than or equal to about 10 mole percent. In some such embodiments, ₂ O ₃ concentration in the glass of the composition B may be greater than or equal to about 6 mole percent and less than or equal to about 9 mole percent, or even less than or equal to about 8 mole%. The B ₂ O ₃ concentration in the glass composition may even be less than or equal to 7 mol%.

The glass composition described herein may further comprise a divalent oxide MO, wherein M is an alkaline earth metal (such as Mg, Ca, Ba, and Sr) and/or Zn. The divalent oxide improves the melting behavior of the glass composition but increases the average coefficient of thermal expansion. When the divalent oxide includes an alkaline earth metal oxide, the alkaline earth metal oxide does not increase the average thermal expansion coefficient of the glass composition as much as the alkali metal oxide contained in the glass composition. However, the divalent oxide also reduces the mobility of the alkali ions in the glass, thereby reducing the ion exchangeability of the glass composition.

Due to the introduction of divalent oxides, the reduction in ion exchangeability of the glass can be offset by replacing the divalent oxides CaO and MgO with an alkali metal oxide Na ₂ O, which increases the average of the glass composition. The coefficient of thermal expansion and improved ion exchangeability of the glass composition. However, substituting Na ₂ O for both the divalent oxide CaO and the alkali metal oxide K ₂ O minimizes the increase in CTE and simultaneously improves the ion exchangeability of the glass composition.

The reduction in ion exchangeability is particularly pronounced when larger divalent oxides such as CaO and BaO are included in the glass composition. Therefore, in order to maintain good ion exchangeability, the concentration of CaO and BaO in the glass composition is minimized. In contrast, the addition of the divalent oxides MgO and ZnO minimizes the adverse effect of the divalent oxide on the alkaline diffusivity, and in this regard, only minimizes the ion exchange performance of the glass composition. In addition, MgO and ZnO do not increase the CTE of the glass composition much more than CaO and BaO. For example, Figure 3 graphically depicts the layer depth and CTE (y-axis) as a function of the substitution of ZnO for CaO (x-axis) in the glass composition. The layer depth was determined after ion exchange of the glass in a KNO ₃ salt bath at 410 ° C for 8 hours. As shown in Fig. 3, as CaO is replaced by ZnO, the depth of the layer of compressive stress increases and the CTE of the glass article decreases.

Further, MgO and/or ZnO may be substituted for B ₂ O ₃ to maintain the melting performance of the glass composition while improving ion exchange efficiency and only minimally increasing CTE. However, when the concentration of MgO and ZnO in the glass composition is high, MgO and ZnO tend to form forsterite (Mg ₂ SiO ₄ ) and zinc spinel (ZnAl ₂ O ₄ ), forsterite (Mg ₂ SiO, respectively). ₄ ) Increasing the liquidus temperature of the glass composition and reducing the meltability of the glass with both zinc spinel (ZnAl ₂ O ₄ ).

In the embodiments described herein, the total concentration of divalent oxide MO (i.e., Mg, Ca, Ba, and Zn) is greater than or equal to about 3 mole percent and less than or equal to about 11 mole percent. In some such embodiments, the total concentration of divalent oxide MO is less than or equal to 9 mole %, for example, when the divalent oxide is present at a concentration greater than or equal to 3 mole % and less than or equal to 9 mole % Time. In some implementations In one example, the concentration of the divalent oxide MO is greater than or equal to 7 mol% and less than or equal to 9 mol%.

As described above, the divalent oxide MO includes a combination of oxides of Mg, Ca, Ba, Sr, and Zn and oxides of Mg, Ca, Ba, Sr, and Zn. ZnO may be present in the glass composition at a concentration greater than or equal to about 0 mole percent and less than or equal to about 3 mole percent or even at a concentration greater than or equal to about 1 mole percent and less than or equal to about 2 mole percent. The MgO may be present in the glass composition at a concentration greater than or equal to about 0 mole percent and less than or equal to about 11 mole percent or even at a concentration greater than or equal to about 5 mole percent and less than or equal to about 10 mole percent. CaO may be present in the glass composition at a concentration greater than or equal to about 0 mole percent and less than or equal to about 8 mole percent or even at a concentration greater than or equal to about 2 mole percent and less than or equal to about 5 mole percent. BaO may be present in the glass composition at a concentration greater than or equal to about 0 mole percent and less than or equal to about 5 mole percent or even at a concentration greater than or equal to about 1 mole percent and less than or equal to about 2 mole percent.

In some embodiments where the divalent oxide comprises both MgO and CaO, the MgO concentration in the glass composition can be greater than the CaO concentration in order to improve ion exchange performance and reduce the CTE of the glass composition. For example, in some embodiments in which the divalent oxide comprises both MgO and CaO, the MgO concentration can be greater than or equal to about 5 mole percent and the CaO concentration is less than about 5 mole percent.

Similarly, in some embodiments where the divalent oxide comprises both ZnO and CaO, the concentration of ZnO in the glass composition can be greater than the CaO concentration in order to improve ion exchange performance and reduce the CTE of the glass composition.

The glass compositions described herein optionally include one or more fining agents. For example, the fining agent may include a combination of SnO ₂ , As ₂ O ₃ , Sb ₂ O _{3 ,} and SnO ₂ , As ₂ O ₃ , and Sb ₂ O ₃ . The fining agent may be present in the glass composition in an amount greater than or equal to about 0 mole percent and less than or equal to about 0.7 mole percent. In an exemplary embodiment, the fining agent is SnO ₂ . SnO ₂ may be present in the glass composition at a concentration greater than or equal to about 0 mole percent and less than or equal to about 0.7 mole percent. In such embodiments, SnO ₂ may be present in the glass composition at a concentration greater than about 0 mole percent and less than or equal to about 0.7 mole percent or even less than or equal to about 0.15 mole percent.

The glass compositions described herein generally have an average coefficient of thermal expansion (CTE) of less than or equal to about 55 x 10 ^-7 / ° C from 20 ° C to 300 ° C. In some embodiments, the CTE of the glass composition can be less than or equal to about 50 x 10 ^-7 / ° C in the range from 20 ° C to 300 ° C. In other embodiments, the CTE of the glass composition can be less than or equal to about 45 x 10 ^-7 / ° C in the range from 20 ° C to 300 ° C. The relatively low CTE value of the glass composition is due, at least in part, to the relatively low total alkali content of the glass composition. These relatively low CTEs make the glass composition particularly well suited for use as a glass cover for molten laminated glass articles. In particular, when the low CTE glass cover layer and the glass core layer having a higher CTE are paired during the melt layer pressing process, the difference in the CTE of the glass core layer and the glass cover layer results in the glass cover layer after cooling The formation of compressive stress. Thus, the glass compositions described herein can be used to form a reinforced laminated glazing article.

The glass compositions described herein are also subjected to ion exchange strengthening. Ion by ion-exchanged glass article described herein to determine the effectiveness of the composition of the glass exchange, the ion exchanged glass article in a KNO ₃ molten salt bath at a temperature of 410 deg.] C for 8 hours to form the glass composition. Thereafter, the compressive stress and the layer depth are measured by optical birefringence. In the examples of the glass compositions described herein, the glass composition generally has a compressive stress greater than 400 MPa after ion exchange under the conditions described above. In some embodiments, the compressive stress can be greater than or equal to about 450 MPa or even greater than or equal to about 500 MPa. In some embodiments, the compressive stress can be greater than or equal to about 550 MPa. Further, the depth of the layer of compressive stress is substantially greater than or equal to about 5 μm or even greater than or equal to about 10 μm.

Further, the glass compositions described herein have liquid phase viscosities suitable for use in melt formation, such as by a melt down draw process and/or a melt layer press process. In particular, the glass compositions described herein have a liquid phase viscosity greater than or equal to about 35,000 Poise (35 kPoise). In some embodiments, the liquid phase viscosity is greater than or equal to 50 kPoise or even greater than or equal to 100 kPoise.

Based on the above, it should be understood that various embodiments of low CTE, ion exchangeable glass compositions are disclosed herein. In a first exemplary embodiment, the glass composition comprises from about 65 mole % to about 70 mole % SiO ₂ as a glass network former, from about 9 mole % to about 14 mole % Al ₂ O ₃ and from about 0 mole % to about 11 mole % B ₂ O ₃ . The glass composition may also include from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K. The glass composition may also include from about 3 mole % to about 11 mole % of the divalent oxide MO, wherein M is at least one of Mg, Ca, Ba, and Zn. The glass composition generally has an average thermal expansion coefficient of less than or equal to 55×10 ^-7 /° C. of the glass formed of the glass composition, and the glass composition after ion exchange for 8 hours in a 100% KNO ₃ salt bath at 410 ° C The compressive stress is greater than or equal to 400 MPa and greater than or equal to the liquid viscosity of 35 kPoise.

In a second exemplary embodiment, the glass composition comprises from about 65 mole % to about 68 mole % SiO ₂ as a glass network former, from about 10 mole % to about 13 mole % Al ₂ O ₃ and from about 6 mole % to about 9 mole % B ₂ O ₃ . The glass composition may also include from about 6 mole % to less than 9 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K. The glass composition may also include from about 7 mole % to about 10 mole % of the divalent oxide MO, wherein M is at least one of Mg, Ca, Ba, and Zn. The glass composition generally has an average thermal expansion coefficient of less than or equal to 55×10 ^-7 /° C. of the glass formed of the glass composition, and the ion exchange in the 100% KNO ₃ salt bath at 410° C. is greater than or after 8 hours. The compressive stress in a glass composition equal to 400 MPa and greater than or equal to the liquid viscosity of 35 kPoise.

In a third exemplary embodiment, the glass composition comprises from about 65 mole % to about 70 mole % SiO ₂ as a glass network former, from about 9 mole % to about 14 mole % Al ₂ O ₃ and from about 0 mole % to about 7 mole % B ₂ O ₃ . The glass composition may also include from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K. The glass composition may also include from about 3 mole % to about 11 mole % of the divalent oxide MO, wherein M is at least one of Mg, Ca, Ba, and Zn. The glass composition generally has an average thermal expansion coefficient of less than or equal to 55×10 ^-7 /° C. of the glass formed of the glass composition, and the glass composition after ion exchange for 8 hours in a 100% KNO ₃ salt bath at 410 ° C The compressive stress is greater than or equal to 400 MPa and greater than or equal to the liquid viscosity of 35 kPoise.

In the fourth exemplary embodiment, the glass composition includes forming the body from about 65 mole% to about 70 mole% of SiO _2, from about 9 to about 14 mole% mole% of Al as a glass web ₂ O ₃ and from about 0 mole % to about 11 mole % B ₂ O ₃ . The glass composition may also include from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K. The glass composition may also include from about 3 mole % to about 9 mole % of the divalent oxide MO, wherein M is at least one of Mg, Ca, Ba, and Zn. The glass composition generally has an average thermal expansion coefficient of less than or equal to 55×10 ^-7 /° C. of the glass formed of the glass composition, and the glass composition after ion exchange for 8 hours in a 100% KNO ₃ salt bath at 410 ° C The compressive stress is greater than or equal to 400 MPa and greater than or equal to the liquid viscosity of 35 kPoise.

In the fifth exemplary embodiment, the glass composition includes forming the body from about 65 mole% to about 70 mole% of SiO _2, from about 9 to about 14 mole% mole% of Al as a glass web ₂ O ₃ and from about 0 mole % to about 11 mole % B ₂ O ₃ . The glass composition may also include from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K. The glass composition may also include from about 3 mole % to about 11 mole % of the divalent oxide MO, wherein MO comprises MgO and CaO, and the MgO concentration (% by mole) is greater than the CaO concentration (% by mole). The glass composition generally has an average thermal expansion coefficient of less than or equal to 55×10 ^-7 /° C. of the glass formed of the glass composition, and the glass composition after ion exchange for 8 hours in a 100% KNO ₃ salt bath at 410 ° C The compressive stress is greater than or equal to 400 MPa and greater than or equal to the liquid viscosity of 35 kPoise.

In a sixth exemplary embodiment, the glass composition comprises from about 65 mole % to about 70 mole % SiO ₂ as a glass network former, from about 9 mole % to about 14 mole % Al ₂ O ₃ and from about 0 mole % to about 11 mole % B ₂ O ₃ . The glass composition may also include from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K. The glass composition can also include from about 3 mole % to about 11 mole % of the divalent oxide MO, wherein MO comprises MgO and CaO, and the MgO concentration is greater than 5 mole % and the CaO concentration is less than 5 mole %. The glass composition generally has an average thermal expansion coefficient of less than or equal to 55×10 ^-7 /° C. of the glass formed of the glass composition, and the glass composition after ion exchange for 8 hours in a 100% KNO ₃ salt bath at 410 ° C The compressive stress is greater than or equal to 400 MPa and greater than or equal to the liquid viscosity of 35 kPoise.

In the seventh exemplary embodiment, the glass composition includes forming the body from about 55 mole% to about 70 mole% of SiO _2, from about 9 to about 14 mole% mole% of Al as a glass web ₂ O ₃ and from about 0 mole % to about 11 mole % B ₂ O ₃ . The glass composition may also include from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K. The glass composition may also include from about 3 mole % to about 11 mole % of the divalent oxide MO, wherein M is at least one of Mg, Ca, Ba, and Zn. In this embodiment, the B ₂ O ₃ concentration can be less than about 7 mole %. In this embodiment, the divalent oxide MO concentration can be less than 9 mole %. The divalent oxide MO may comprise both MgO and CaO, and the MgO concentration (% by mole) may be greater than the CaO concentration (% by mole), such as when the MgO concentration is greater than about 5 mole % and the CaO concentration is less than 5 mole % . The glass composition generally has an average thermal expansion coefficient of less than or equal to 55×10 ^-7 /° C. of the glass formed of the glass composition, and the glass composition after ion exchange for 8 hours in a 100% KNO ₃ salt bath at 410 ° C The compressive stress is greater than or equal to 400 MPa and greater than or equal to the liquid viscosity of 35 kPoise.

Although the exemplary glass compositions have been described above with reference to specific component ranges of various constituent components of each glass composition (such as SiO ₂ , Al ₂ O ₃ , B ₂ O _{3 ,} etc.), it should be understood that each composition Each component of the component may include one or more narrower component ranges of the component, as described above. It is further understood that the narrower range of constituent components and/or the relationship between the various constituent components can be incorporated into any of the embodiments of the glass compositions described herein to produce the desired properties. glass.

Referring now to Figure 4, the glass composition described herein can be used to form a glass article, such as laminated glass article 100 schematically depicted in cross-section in Figure 4. The laminated glazing article 100 generally comprises a glass core layer 102 and a pair of glass cover layers 104a, 104b. Due to the relatively low coefficient of thermal expansion of the glass compositions described herein, such glass compositions are particularly well suited for use as a glass cover layer, as will be described in greater detail herein.

4 illustrates a glass core layer 102 that includes a first surface 103a and a second surface 103b that is opposite the first surface 103a. The first glass cover layer 104a is fused to the first surface 103a of the glass core layer 102, and the second glass cover layer 104b is fused to the second surface 103b of the glass core layer 102. The glass cover layers 104a, 104b are fused to the glass core layer 102 without the need to place any additional material (such as adhesives, coatings, etc.) between the glass core layer 102 and the glass cover layers 104a, 104b. Thus, the first surface of the glass core layer is directly adjacent to the first glass cover layer and the second surface of the glass core layer is directly adjacent to the second glass cover layer. In a In some embodiments, the glass core layer 102 and the glass cover layers 104a, 104b are formed via a melt lamination process. A diffusion layer (not shown) may be formed between the glass core layer 102 and the glass cover layer 104a, or between the glass core layer 102 and the glass cover layer 104b or both. In this case, the average coverage thermal expansion coefficient of the first diffusion layer has a value between the value of the average coverage thermal expansion coefficient of the core and the value of the average coverage thermal expansion coefficient of the first cladding layer; or the average coverage thermal expansion of the second diffusion layer The coefficient has a value between the value of the average coverage thermal expansion coefficient of the core and the value of the average coverage thermal expansion coefficient of the second cover layer.

In an embodiment of the laminated glazing article 100 described herein, a glass cover layer 104a, 104b is formed from the first glass composition, the first glass composition having an average coverage thermal expansion coefficient CTE _coverage ; and a different second glass The composition forms a glass core layer 102 having an average core thermal expansion coefficient CTE _core . The CTE _{core is} larger than the CTE _coverage , resulting in the glass cover layers 104a, 104b being compressively stressed without ion exchange or thermal tempering.

In particular, the glass article 100 described herein can be formed by a molten layer press process, such as the process described in U.S. Patent Application Serial No. 4,214,886, the disclosure of which is incorporated herein by reference. By way of example with reference to Figure 5, a laminated melt drawing apparatus 200 for forming a laminated glazing article includes a thermally insulated tube 202 over the lower insulating tube 204. The upper insulated tube 202 includes a trough 210 into which the molten glass cover composition 206 is fed from a fuser (not shown). Similarly, the lower insulated tube 204 includes a trough 212 into which the molten glass core composition 208 is fed from a melter (not shown). In the embodiments described herein, the molten glass core composition 208 has an average core thermal expansion coefficient CTE _core that is greater than the average coverage thermal expansion coefficient CTE _coverage of the molten glass cover composition 206.

As the molten glass core composition 208 fills the trough 212, the molten glass core composition 208 overflows the trough 212 and flows over the outer forming surfaces 216, 218 of the lower insulated tube 204. The outer forming surfaces 216, 218 of the lower insulating tube 204 converge at the root 220. Thus, the molten glass core composition 208 flowing over the outer forming surfaces 216, 218 is rejoined at the root 220 of the lower insulating tube 204, thereby forming the glass core layer 102 of the laminated glass article.

At the same time, the molten glass cover composition 206 overflows the grooves 210 formed in the upper heat insulating tube 202 and flows over the outer forming surfaces 222, 224 of the upper heat insulating tube 202. The molten glass cover composition 206 is outwardly offset by the upper insulating tube 202 such that the molten glass cover composition 206 flows around the lower insulating tube 204 and melts over the surface 216, 218 formed on the outside of the lower insulating tube. The glass core composition 208 is contacted, fused to the molten glass core composition and forms a glass cover layer 104a, 104b around the glass core layer 102.

As described above, the molten glass core composition 208 generally has an average core thermal expansion coefficient CTE _core that is greater than the average coverage thermal expansion coefficient CTE _coverage of the molten glass cover composition 206. Therefore, when the glass core layer 102 and the glass cover layers 104a, 104b are cooled, the differential compressive stress of the thermal expansion coefficients of the glass core layer 102 and the glass cover layers 104a, 104b develops in the glass cover layers 104a, 104b. The compressive stress increases the strength of the resulting laminated glass article.

Referring again to the laminated glazing article 100 depicted in Figure 4, the glass composition having a relatively low average coefficient of thermal expansion (such as having a temperature range of from about 20 ° C to about 300 ° C less than or equal to 55 x 10 as described herein). The glass composition of the thermal expansion coefficient of ^-7 / ° C) forms the glass cover layers 104a, 104b of the laminated glass article 100.

For example, in one embodiment, a glass cover layer is formed from a glass composition having a low CTE, such as the glass composition described above, which includes from a composition of about 65 as a glass network former. Molar% to about 70 mole % SiO ₂ , from about 9 mole % to about 14 mole % Al ₂ O ₃ and from about 0 mole % to about 11 mole % B ₂ O ₃ ; From about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na and K; from about 3 mole % to about 11 mole % of divalent oxidation And MO, wherein M is at least one of Mg, Ca, Ba, and Zn. The glass compositions generally have an average coefficient of thermal expansion of less than or equal to 55 x 10 ^-7 / ° C in a temperature range from about 20 ° C to about 300 ° C and are subjected to ion exchange strengthening. Due to the relatively low average coefficient of thermal expansion, the glass composition is particularly well suited for use as a glass cover for laminated glass articles.

In another exemplary embodiment, a glass cover layer is formed from a glass composition having a low CTE, such as the glass composition described above, which includes about 65 moles as a glass network former. 5% to about 68 mole % SiO ₂ , from about 10 mole % to about 13 mole % Al ₂ O ₃ and from about 6 mole % to about 9 mole % B ₂ O ₃ ; 6 mole % to less than 9 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na and K; and from about 7 mole % to about 10 mole % of divalent oxidation And MO, wherein M is at least one of Mg, Ca, Ba, and Zn. The glass compositions generally have an average coefficient of thermal expansion of less than or equal to 55 x 10 ^-7 / ° C in a temperature range from about 20 ° C to about 300 ° C and are subjected to ion exchange strengthening.

Although specific glass compositions for the glass cover layers 104a, 104b have been described herein, it should be understood that any of the glass compositions described herein can be used to form the laminated glass article 100 due to the relatively low CTE of the glass composition. The glass cover layers 104a, 104b.

Further, although the glass cover layers 104a, 104b of the laminated glass article 100 have been described above as being formed of a glass composition having a relatively low average coefficient of thermal expansion, the glass core layer 102 of the glass article 100 has a higher than glass coverage. The glass composition of the average coefficient of thermal expansion of layers 104a, 104b is formed to promote the development of compressive stress in the cover layer after cooling the laminated article after melt formation. For example, a glass core layer can be formed from a glass composition comprising an alkali ion, such as in U.S. Patent Application entitled "High CTE Potassium Borosilicate Core Glasses and Glass Articles Comprising the Same", to Corning Incorporated A glass composition as described in No. 61/604,869, having a coefficient of thermal expansion greater than or equal to 75 x 10 ^-7 / ° C in a temperature range from 20 ° C to 800 ° C. For example, the core glass layer can be formed from a glass composition comprising from about 70 mole % to about 80 mole % SiO ₂ ; from about 0 mole % to about 8 mole % Al ₂ O ₃ ; From about 3 mole % to about 10 mole % B ₂ O ₃ ; from about 0 mole % to about 2 mole % Na ₂ O; from about 10 mole % to about 15 mole % K ₂ O; and from about 5 mol% to about 6 mol% of an alkaline earth metal oxide, wherein the alkaline earth metal oxide is at least one of CaO, SrO and BaO and does not contain MgO. It should be understood, however, that as long as the average coefficient of thermal expansion of the glass core layer 102 is greater than the average coefficient of thermal expansion of the glass cover layers 104a, 104b, other glass compositions can be used to form the glass core layer 102 of the laminated glass article 100.

After formation, the laminated glass article can be ion exchange strengthened to further increase surface compression in the glass cover layers 104a, 104b. In such embodiments, the ion-exchange strengthened glass article stack 100 for 8 hours in KNO ₃ molten salt bath at a temperature of 410 deg.] C. After removal from the salt bath, the glass article has a compressive stress greater than or equal to 400 MPa. In some embodiments, the compressive stress can be greater than or equal to about 450 MPa or even greater than or equal to about 500 MPa.

Instance

Examples of the glass compositions described herein will be further clarified by the following examples.

A plurality of exemplary glass compositions were prepared according to the ingredient compositions listed in Tables 1 through 6 below. The ingredients of the oxide component are mixed, melted and formed into a glass plate. The properties of the glass melt (i.e., liquid phase viscosity, liquidus temperature, annealing point, etc.) were measured and the results are reported in Tables 1 to 6. After formation into a glass plate, the samples were ion exchanged in a KNO ₃ salt bath at a temperature of 410 ° C for 8 hours. Layer depth and compressive stress generated by optical birefringence measurements. The results of compressive stress and layer depth measurement are reported in Tables 1 to 6. The "A" samples (ie, samples A1, A2, etc.) have a coefficient of thermal expansion of less than or equal to 55 x 10 ^-7 / ° C, a compressive stress greater than or equal to 400 MPa, and a liquid viscosity greater than or equal to 35 kPoise. The "C" samples (ie, samples C1, C2, etc.) do not meet these criteria (ie, an average thermal expansion coefficient less than or equal to 55 × 10 ^-7 / ° C, a compressive stress greater than or equal to 400 MPa or greater than or equal to At least one of the liquid viscosity of 35 kPoise, and for that reason, the "C" sample is present herein as a comparative, non-inventive example.

Examples A11, A17, A18, and A25 are of particular interest for the various exemplary "A" compositions listed in Tables 1 through 6. Each of the compositions has an average thermal expansion coefficient of less than or equal to 55 x 10 ^-7 / ° C, a compressive stress greater than or equal to 400 MPa, and a liquid viscosity greater than or equal to 35 kPoise. In particular, Example A11 is a lithium-containing glass having a CTE of 44.6 x 10 ^-7 / ° C and a liquid viscosity of greater than 300 kPoise. After ion exchange strengthening, Example A11 had a surface compressive stress of approximately 560 MPa. This composition combines a particularly low CTE with a particularly high surface compressive stress.

Example A17 is a glass containing sodium having a CTE of 50 x 10 ^-7 / ° C and a liquid viscosity of greater than 249 kPoise. Example A17 has a surface compressive stress of approximately 475 MPa, similar to a plurality of other "A" compositions. However, Example A17 has a layer depth greater than 11 μm. This indicates that for a given surface compression, the glass composition of Example A17 can be ion exchanged over a shorter period of time than other glass compositions, thereby improving the manufacturing yield. The deep layer depth of this glass is obtained from the monovalent cation oxide having MgO as the glass composition. Although all divalent cation oxides reduce the depth of the layer, MgO reduces the layer depth to a lesser extent than CaO and BaO.

Example A18 is also a glass containing sodium having a CTE of 52.8 x 10 ^-7 / ° C and a liquid viscosity of greater than 300 kPoise. Example A18 also has a surface compressive stress of approximately 490 MPa and a layer depth of approximately 9 μm. The nature of this glass contributes to the relatively low B ₂ O ₃ content of this glass composition.

Example A25 is also a glass containing sodium having a CTE of 49.5 x 10 ^-7 / ° C and a liquid viscosity of greater than 134 kPoise. Example A25 also has a relatively high surface compressive stress of approximately 545 MPa and a relatively deep layer depth of approximately 9.9 μm. The nature of this glass contributes to the fact that this glass composition is substantially free of K ₂ O and contains MgO as the sole divalent cation oxide.

It should now be understood that the glass compositions described herein have a relatively low coefficient of thermal expansion. In this regard, the glass compositions described herein are particularly well suited for use in combination with glass compositions having a relatively high coefficient of thermal expansion. A compressively stressed laminated glass article is formed by a melt lamination process. The glass objects can be used in a variety of consumer electronic devices, including but not limited to: mobile phones, personal music players, tablets, LCD and LED displays, automated teller machines, and the like.

It should also be understood that the properties of the glass compositions described herein (eg, liquid phase viscosity, liquidus temperature, etc.) make the glass composition well suited for use with the melt forming process, such as a melt down draw process or a melt layer press process. .

Furthermore, the glass compositions described herein are subjected to enhanced by ion exchange. In this regard, the strength of the laminated glass article used as the glass cover layer of the glass composition described herein can be further improved by laminating the glass article after lamination. Such glass articles are particularly well suited for use as a cover glass for touch screen displays, mobile electronic devices, and the like.

Further, although a specific reference has been made herein to the use of a glass composition as a cover layer for a laminated glass article, it will be appreciated that the glass composition can also be used to separately form a glass article (ie, a non-laminated glass article). Such as, for example, cover glass for electronic devices and other similar glass objects.

It will be apparent to those skilled in the art that various modifications and changes may be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Therefore, the present specification is intended to cover such modifications and modifications as the scope of the appended claims and the scope of the claims.

Claims (29)

A glass composition comprising: from about 65 mole % to about 70 mole % SiO ₂ ; from about 9 mole % to about 14 mole % Al ₂ O ₃ ; from about 0 moles %至约11摩尔% B ₂ O ₃ ; from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na and K; From about 3 moles to about 11 mole % of the divalent oxide MO, wherein M is at least one of Mg, Ca, Ba, SrO, and Zn, wherein an average thermal expansion of one of the glasses formed from the glass composition The coefficient is less than or equal to 55×10 ^-7 /°C, and the compressive stress of one of the glass compositions after ion exchange for 8 hours in a 100% KNO ₃ salt bath at 410 ° C is greater than or equal to 400 MPa, and one liquid The phase viscosity is greater than or equal to 35 kPoise. The glass composition of claim 1 wherein the glass composition comprises: from about 65 mole % to about 68 mole % SiO ₂ ; from about 10 mole % to about 13 mole % of Al ₂ O ₃ ; from about 6 mole% to about 9 mole% B ₂ O ₃ ; from about 6 mole % to less than 9 mole % of the alkali metal oxide R ₂ O, wherein R is Li, Na and K At least one of; and from about 7 moles to about 10 mole% of the divalent oxide MO, wherein M is at least one of Mg, Ca, and Zn. The glass composition of claim 1 wherein the concentration of one of B ₂ O ₃ is less than about 7 mole %. The glass composition of claim 1, wherein one of the divalent oxides MO has a concentration of less than 9 mol%. The glass composition according to claim 1, wherein the divalent oxide MO comprises MgO and CaO, and one of the concentrations of MgO (% by mole) is greater than a concentration of CaO (% by mole). The glass composition according to claim 1, wherein the divalent oxide MO comprises MgO and CaO, and a concentration of MgO (% by mole) is greater than 5 mol% and a concentration of CaO (% by mol) is less than 5 Moer%. The glass composition of claim 1, wherein the glass composition is strengthened by ion exchange. The glass composition according to claim 1, wherein the glass composition further comprises at least one of SnO ₂ , As ₂ O ₃ and Sb ₂ O ₃ as a fining agent. The glass composition of claim 8, wherein the fining agent is SnO ₂ , and the SnO ₂ is present in the glass composition at a concentration of greater than 0 mol% and less than or equal to about 0.7 mol%. A glass article comprising: a glass core layer disposed between a first glass cover layer and a second glass cover layer, wherein the first glass cover layer and the second glass cover layer Formed from a glass composition comprising: from about 55 mole % to about 70 mole % SiO ₂ ; from about 9 mole % to about 14 mole % Al ₂ O ₃ ; from about 0 From about 5 moles to about 2 moles of B ₂ O ₃ ; from about 5 mole % to less than 10 mole % of the alkali metal oxide R ₂ O, wherein R is at least one of Li, Na, and K; And a divalent oxide MO from about 3 mole % to about 11 mole %, wherein M is at least one of Mg, Ca, Ba, SrO, and Zn. The glass article of claim 10, wherein the first glass cover layer and the second glass cover layer comprise greater than 65 mole % SiO ₂ . The glass article of claim 10, wherein the concentration of one of the B ₂ O ₃ in the first glass cover layer and the second glass cover layer is less than about 7 mole %. The glass article of claim 10, wherein the concentration of one of the divalent oxides MO in the first glass cover layer and the second glass cover layer is less than about 9 mole %. The glass article of claim 10, wherein the divalent oxide MO comprises MgO and CaO, and one of the concentrations of MgO (% by mole) is greater than a concentration of CaO (% by mole). The glass article of claim 10, wherein the divalent oxide MO comprises MgO and CaO, and one of the concentrations of MgO is greater than 5 mol% and a concentration of CaO is less than 5 mol%. The glass article of claim 10, wherein the first glass cover layer and the second glass cover layer are ion exchange reinforced. The glass article of claim 10, wherein the first glass cover layer and the second glass cover layer have a compressive stress greater than or equal to 400 MPa. The glass article of claim 10, wherein: the glass core layer has an average core thermal expansion coefficient CTE _core ; and the first glass cover layer and the second glass cover layer have an average coverage thermal expansion coefficient CTE _coverage , the average The coverage thermal expansion coefficient CTE _{coverage is} less than the average core thermal expansion coefficient CTE _core . The glass article according to the request 18, which covers the average coefficient of thermal expansion CTE to _cover from the inner one 20 ℃ 300 ℃ temperature range is less than or equal to 55 × 10 ^-7 / ℃. The glass article of claim 10, wherein the first glass cover layer and the second glass cover layer are compressively stressed. The glass article of claim 10, wherein the first glass cover layer and the second glass cover layer further comprise at least one of SnO ₂ , As ₂ O ₃ and Sb ₂ O ₃ as a fining agent. The glass article of claim 21, wherein the clarifying agent is SnO ₂ , and the SnO ₂ is present in the first glass cover layer and the second at a concentration greater than 0% by mole and less than or equal to about 0.7% by mole. In the glass cover. The glass article of any one of claims 10 to 22, wherein one of the first surfaces of the glass core layer is directly adjacent to the first glass cover layer, and wherein the second surface of one of the glass core layers is directly adjacent The second glass cover layer. The glass article of any one of claims 10 to 22, wherein a first diffusion layer is disposed between the first glass cover layer and the glass core layer. The glass article of claim 24, wherein the average coverage thermal expansion coefficient of the first diffusion layer has a value between an average coverage thermal expansion coefficient of one of the cores and an average coverage thermal expansion coefficient of the first cladding layer. a value. The glass article of claim 24, wherein a second diffusion layer is disposed between the second glass cover layer and the glass core layer. The glass article of claim 26, wherein the average coverage thermal expansion coefficient of the second diffusion layer has a value between an average coverage thermal expansion coefficient of one of the cores and an average coverage thermal expansion coefficient of one of the second cladding layers a value. A glass composition according to any one of claims 1 to 9 for use in a shield for consumer or commercial electronic devices including LCDs and LED displays, computer monitors, automated teller machines (ATMs) Glass or glass backplane applications; for touchscreen or touch sensor applications; for portable electronic devices including mobile phones, personal media players and tablets; for optoelectronic applications; for architectural glass applications; Used in automotive or vehicle glass applications; or for commercial or household appliance applications. A glass article according to any one of claims 10 to 22 for use in a cover glass or glass backsheet in a consumer or commercial electronic device comprising an LCD and an LED display, a computer monitor, an automated teller machine (ATMs) Applications; for touch screen or touch sensor applications; for portable electronic devices including mobile phones, personal media players and tablets; for optoelectronic applications; for architectural glass applications; for cars or vehicles Glass applications; or for commercial or household appliance applications.